JP2020503402A - Thermoplastic resin composition and molded article produced therefrom - Google Patents

Abstract

The thermoplastic resin composition of the present invention comprises about 100 parts by weight of a thermoplastic resin containing a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin; about 10 parts by weight to about 30 parts by weight of an antistatic agent; And about 0.01 parts by weight to about 2 parts by weight of zinc oxide, wherein the antistatic agent comprises one or more of a polyetheresteramide block copolymer, a polyalkylene glycol, and a polyamide. . The thermoplastic resin composition is excellent in antibacterial properties, antistatic properties, impact resistance and the like.

Description

  The present invention relates to a thermoplastic resin composition and a molded article produced therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent antibacterial properties, antistatic properties, impact resistance, and the like, and a molded article produced therefrom.

  As thermoplastic resins, rubber-modified aromatic vinyl copolymer resins such as acrylonitrile-butadiene-styrene copolymer resin (ABS resin) are excellent in mechanical properties, workability, appearance characteristics, etc., and are used for electric / electronic products. Widely used for interior / exterior materials of automobiles, interior / exterior materials of automobiles, exterior materials for buildings, etc.

  When these resins are used in applications where physical contact occurs, such as medical equipment, toys, food containers, etc., the materials themselves are required to have antibacterial properties that can remove or suppress bacteria, and It is required to have mechanical properties such as antistatic property and impact resistance for preventing the occurrence of cracks. In order to obtain an antibacterial thermoplastic resin composition, an inorganic or organic antibacterial agent may be used.However, in the case of an inorganic antibacterial agent, there are problems such as discoloration of the thermoplastic resin, reduction in transparency, and the like, and an organic antibacterial agent. In the case of (1), application is not easy because there is a risk of decomposition and elution during high-temperature processing.

  Therefore, there is a need to develop a thermoplastic resin composition having not only antibacterial properties but also excellent antistatic properties and impact resistance.

  The background art of the present invention is disclosed in Japanese Patent Application Laid-Open No. 2005-239904.

  An object of the present invention is to provide a thermoplastic resin composition having excellent antibacterial properties, antistatic properties, impact properties, and the like.

  Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.

  The above and other objects of the present invention can all be achieved by the present invention described below.

  One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition comprises about 100 parts by weight of a thermoplastic resin containing a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin; about 10 parts by weight to about 30 parts by weight of an antistatic agent; And about 2 parts by weight of zinc, and the antistatic agent comprises one or more of a polyetheresteramide block copolymer, a polyalkylene glycol, and a polyamide.

  In a specific example, the rubber-modified vinyl-based graft copolymer may be a rubbery polymer obtained by graft-polymerizing a monomer mixture containing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer. .

  In a specific example, the aromatic vinyl copolymer resin may be a polymer of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.

  In a specific example, the rubber-modified vinyl-based graft copolymer is included in about 20% by weight to about 50% by weight based on 100% by weight of the thermoplastic resin, and the aromatic vinyl-based copolymer resin is It may comprise from about 50% to about 80% by weight of 100% by weight of the thermoplastic resin.

In an embodiment, the zinc oxide has an average particle size is about 0.2μm~ about 3 [mu] m, BET specific surface area may be about ^{1 m} 2 / g to about ^{10 m} 2 / g.

  In a specific example, the zinc oxide has an intensity ratio (B / A) of a peak A in a 370 nm to 390 nm region and a peak B in a 450 nm to 600 nm region when photoluminescence (Photo Luminescence) is measured, from about 0 to about 1. possible.

  In a specific example, the zinc oxide has a peak position (peak position) 2θ value in the range of 35 ° to 37 ° upon X-ray diffraction (X-ray diffraction, XRD) analysis, and has a crystallite size according to the following formula 1. The value of (crystallite size) can be from about 1,000 to about 2,000:

  In the above formula 1, K is a shape factor, λ is an X-ray wavelength, β is an FWHM value (degree) of an X-ray diffraction peak (peak), and θ is It is a value of a peak position (peak position degree).

  In a specific example, the above thermoplastic resin composition was inoculated with Staphylococcus aureus and Escherichia coli on a test piece having a size of 5 cm × 5 cm according to JIS Z 2801 antibacterial evaluation method, and cultured at 35 ° C. and RH 90% for 24 hours. After that, the measured antimicrobial activity values can be about 2 to about 7 and about 2 to about 6.5, respectively.

In a specific example, the thermoplastic resin composition may have a surface resistance value of about 1 × 10 ⁶ Ω · cm to about 1 × 10 ¹⁰ Ω · cm based on ASTM D257.

  In a specific example, the thermoplastic resin composition may have a notch Izod impact strength of a 1/4 "thick test piece, measured according to ASTM D256, of about 15 kgf.cm/cm to about 25 kgf.cm/cm.

  Another aspect of the present invention relates to a molded article. The molded article is formed from the thermoplastic resin composition.

  The present invention has the effect of the invention of providing a thermoplastic resin composition having excellent antibacterial properties, antistatic properties, impact resistance, and the like, and a molded article formed therefrom.

  Hereinafter, the present invention will be described in detail.

  The thermoplastic resin composition according to the present invention comprises (A1) a thermoplastic resin containing (A1) a rubber-modified vinyl-based graft copolymer and (A2) an aromatic vinyl-based copolymer resin; (B) an antistatic agent; And (C) zinc oxide.

(A) Thermoplastic resin The thermoplastic resin of the present invention is a rubber-modified vinyl-based copolymer resin containing (A1) a rubber-modified vinyl-based graft copolymer and (A2) an aromatic vinyl-based copolymer resin. Is also good.

(A1) Rubber-Modified Aromatic Vinyl-Based Graft Copolymer The rubber-modified vinyl-based graft copolymer according to one embodiment of the present invention is a rubbery polymer comprising an aromatic vinyl-based monomer and a vinyl cyanide-based monomer. The monomer mixture containing the polymer may be obtained by graft polymerization. For example, the rubber-modified vinyl-based graft copolymer can be obtained by graft-polymerizing a rubber-based polymer with a monomer mixture containing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer. Depending on the above, graft polymerization can be performed by further adding a monomer that imparts processability and heat resistance to the monomer mixture. The above polymerization can be carried out by a known polymerization method such as emulsion polymerization, suspension polymerization and the like. The rubber-modified vinyl-based graft copolymer can form a core (rubber polymer) -shell (copolymer of monomer mixture) structure, but is not limited thereto.

  In specific examples, the rubbery polymer includes diene rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene); saturated rubber obtained by hydrogenating the diene rubber; isoprene rubber; Examples thereof include an alkyl (meth) acrylate rubber having 2 to 10 carbon atoms, a copolymer of alkyl (meth) acrylate having 2 to 10 carbon atoms and styrene, and an ethylene-propylene-diene monomer terpolymer (EPDM). Can be. These can be applied alone or as a mixture of two or more. For example, a diene rubber, a (meth) acrylate rubber, or the like can be used, and specifically, a butadiene rubber, a butyl acrylate rubber, or the like can be used. The rubbery polymer (rubber particles) has an average particle size (Z-average) of about 0.05 μm to about 6 μm, for example, about 0.15 μm to about 4 μm, specifically about 0.25 μm to about 3.5 μm. Can be Within the above range, the thermoplastic resin composition is excellent in impact resistance, appearance characteristics, and the like.

  In a specific example, the content of the rubbery polymer is about 20% to about 70% by weight, for example, about 25% to about 60% by weight, based on 100% by weight of the whole rubber-modified vinyl-based graft copolymer. The content of the monomer mixture (including the aromatic vinyl monomer and the vinyl cyanide monomer) may be about 30% by weight based on 100% by weight of the whole rubber-modified vinyl-based graft copolymer. % To about 80% by weight, for example about 40% to about 75% by weight. Within the above range, the thermoplastic resin composition is excellent in impact resistance, appearance characteristics, and the like.

  In a specific example, the aromatic vinyl monomer can be graft-copolymerized with the rubbery polymer, and may be styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butyl. Styrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene and the like can be exemplified. These can be used alone or as a mixture of two or more. The content of the aromatic vinyl monomer may be about 10% to about 90% by weight, for example, about 40% to about 90% by weight, based on 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition is excellent in workability, impact resistance, and the like.

  In specific examples, the vinyl cyanide-based monomer is a copolymerizable with the aromatic vinyl-based monomer, and includes acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. can do. These can be used alone or as a mixture of two or more. For example, acrylonitrile, methacrylonitrile, and the like can be used. The content of the vinyl cyanide monomer may be about 10% to about 90% by weight, for example, about 10% to about 60% by weight, based on 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition is excellent in chemical resistance, mechanical properties, and the like.

  In specific examples, examples of the monomer for imparting the processability and heat resistance include (meth) acrylic acid, maleic anhydride, and N-substituted maleimide, but are not limited thereto. When a monomer for imparting the above processability and heat resistance is used, its content is about 15% by weight or less, for example, about 0.1% by weight to about 10% by weight in 100% by weight of the monomer mixture. % By weight. Within the above range, processability and heat resistance can be imparted to the thermoplastic resin composition without impairing other physical properties.

  In a specific example, as the rubber-modified vinyl-based graft copolymer, a styrene monomer which is an aromatic vinyl-based compound and an acrylonitrile monomer which is a vinyl cyanide-based compound are grafted onto a butadiene-based rubbery polymer. Copolymer obtained by grafting a styrene monomer, which is an aromatic vinyl compound, and an acrylonitrile monomer, which is a vinyl cyanide compound, to a copolymer (g-ABS) obtained by the above method and a butyl acrylate rubbery polymer. An acrylate-styrene-acrylonitrile graft copolymer (g-ASA) or the like, which is a union, can be exemplified.

  In a specific example, the rubber-modified vinyl-based graft copolymer is about 20% by weight to 100% by weight of the entire thermoplastic resin (rubber-modified vinyl-based graft copolymer and aromatic vinyl-based copolymer resin). It may be included at about 50% by weight, for example from about 25% to about 45% by weight. Within the above range, the thermoplastic resin composition is excellent in impact resistance, fluidity (moldability), appearance characteristics, balance of these physical properties, and the like.

(A2) Aromatic vinyl copolymer resin The aromatic vinyl copolymer resin according to one specific example of the present invention is an aromatic vinyl copolymer used for a general rubber-modified vinyl copolymer resin. It may be a resin. For example, the aromatic vinyl copolymer resin may be a polymer of a monomer mixture containing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.

  In a specific example, the aromatic vinyl-based copolymer resin is obtained by mixing an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer, and then polymerizing the same. The polymerization can be performed by a known polymerization method such as emulsion polymerization, suspension polymerization, or bulk polymerization.

  In a specific example, the aromatic vinyl monomer includes styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, and dichlorostyrene. , Dibromostyrene, vinyl naphthalene and the like can be used. These can be applied alone or as a mixture of two or more. The content of the aromatic vinyl-based monomer may be about 20% by weight to about 90% by weight, for example, about 30% by weight to about 80% by weight, based on 100% by weight of the entire aromatic vinyl-based copolymer resin. . Within the above range, the thermoplastic resin composition is excellent in impact resistance, fluidity, and the like.

  In a specific example, the monomer copolymerizable with the aromatic vinyl monomer may include at least one of a vinyl cyanide monomer and an alkyl (meth) acrylic monomer. For example, a vinyl cyanide monomer or a vinyl cyanide monomer and an alkyl (meth) acrylic monomer, specifically, a vinyl cyanide monomer and an alkyl (meth) acrylic monomer There may be.

  In specific examples, examples of the vinyl cyanide-based monomer include, but are not limited to, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. These can be used alone or as a mixture of two or more. For example, acrylonitrile, methacrylonitrile, and the like can be used.

  In a specific example, examples of the alkyl (meth) acrylic monomer include (meth) acrylic acid and / or an alkyl (meth) acrylate having 1 to 10 carbon atoms. These can be used alone or as a mixture of two or more. For example, methyl methacrylate, methyl acrylate and the like can be used.

  In a specific example, when the monomer copolymerizable with the aromatic vinyl monomer is a mixture of a vinyl cyanide monomer and an alkyl (meth) acrylic monomer, The content of the monomer is about 1% by weight to about 40% by weight, for example, about 2% by weight to about 35% by weight based on 100% by weight of the monomer copolymerizable with the aromatic vinyl monomer. And the content of the alkyl (meth) acrylic monomer is about 60% by weight to about 99% by weight based on 100% by weight of the monomer copolymerizable with the aromatic vinylic monomer. For example, from about 65% to about 98% by weight. Within the above range, the thermoplastic resin composition is excellent in transparency, heat resistance, workability, and the like.

  In a specific example, the content of the monomer copolymerizable with the aromatic vinyl-based monomer is about 10% by weight to about 80% by weight based on 100% by weight of the entire aromatic vinyl-based copolymer resin. It can be from about 20% to about 70% by weight. Within the above range, the thermoplastic resin composition is excellent in impact resistance, fluidity, and the like.

  In a specific example, the aromatic vinyl copolymer resin has a weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) of about 10,000 g / mol to about 300,000 g / mol, for example, about 15, 000 g / mol to about 150,000 g / mol. Within the above range, the thermoplastic resin composition is excellent in mechanical strength, moldability, and the like.

  In a specific example, the aromatic vinyl copolymer resin may be included in about 50% to about 80% by weight, for example, about 55% to about 75% by weight, based on 100% by weight of the entire thermoplastic resin. Within the above range, the thermoplastic resin composition is excellent in impact resistance, fluidity (moldability), and the like.

(B) Antistatic agent The antistatic agent according to one embodiment of the present invention can improve the antibacterial property, antistatic property, and the like of a thermoplastic resin composition (sample) together with a small amount of zinc oxide. And may include polyetheresteramide block copolymers, polyalkylene glycols and polyamides, combinations thereof, and the like. Preferably, a polyetheresteramide block copolymer can be contained, and an antistatic agent composed of a commercially available polyetheresteramide copolymer may be used.

  In a specific example, the polyetheresteramide block copolymer is a reaction comprising an aminocarboxylic acid having 6 or more carbon atoms, a lactam, or a diamine-dicarboxylate; a polyalkylene glycol; and a dicarboxylic acid having 4 to 20 carbon atoms. It may be a block copolymer of a mixture.

  Examples of the salt of an aminocarboxylic acid having 6 or more carbon atoms, a lactam, or a diamine-dicarboxylic acid include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminoperconic acid, ω-aminocapric acid, Aminocarboxylic acids such as 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid, etc .; lactams such as caprolactam, enantholactam, caprylactam, lauryl lactam, etc .; and salts of hexamethylenediamine-adipic acid; A salt of a diamine and a dicarboxylic acid, such as a salt of hexamethylenediamine-isophthalic acid, and the like can be given. For example, 1,2-aminododecanoic acid, caprolactam, hexamethylenediamine-adipic acid salt and the like can be used.

  Examples of the polyalkylene glycol include polyethylene glycol, poly (1,2- and 1,3-propylene glycol), polytetramethylene glycol, polyhexamethylene glycol, a block or random copolymer of ethylene glycol and propylene glycol, ethylene Examples include a copolymer of glycol and tetrahydrofuran. For example, polyethylene glycol, a copolymer of ethylene glycol and propylene glycol, or the like can be used.

  Examples of the dicarboxylic acid having 4 to 20 carbon atoms include terephthalic acid, 1,4-cyclohexacarboxylic acid, sebacic acid, adipic acid, dodecanocarboxylic acid, and the like.

  In a specific example, the bond between the aminocarboxylic acid having 6 or more carbon atoms, lactam, or diamine-dicarboxylate; and the polyalkylene glycol; may be an ester bond, and the aminocarboxylic acid having 6 or more carbon atoms. , A lactam, or a diamine-dicarboxylate; the dicarboxylic acid having 4 to 20 carbon atoms may be an amide bond, the polyalkylene glycol; and the dicarboxylic acid having 4 to 20 carbon atoms; May be an ester bond.

  In a specific example, the above polyetheresteramide block copolymer can be produced by a known synthesis method, for example, the synthesis method disclosed in JP-B-56-45419 and JP-B-55-133424. Can be manufactured by

  In embodiments, the polyetheresteramide block copolymer may include about 10% to about 95% polyether-ester blocks by weight. Within the above range, the thermoplastic resin composition is excellent in mechanical properties, antistatic properties and the like.

  In a specific example, the antistatic agent is used in an amount of about 10 parts by weight to about 30 parts by weight, for example, about 12 parts by weight to about 25 parts by weight, specifically about 14 parts by weight, based on about 100 parts by weight of the thermoplastic resin. Parts to about 20 parts by weight. When the above antistatic agent is used in less than about 10 parts by weight, the antibacterial property and antistatic property of the thermoplastic resin composition may be reduced. When the amount is more than about 30 parts by weight, the impact resistance of the thermoplastic resin composition may be reduced. , The appearance characteristics and the like may be reduced.

(C) Zinc oxide The zinc oxide of the present invention can improve the antibacterial property and the like of the thermoplastic resin composition together with the heat stabilizer, and uses zinc oxide which is usually used in an antibacterial composition. Can be.

In a specific example, the zinc oxide may have an average particle size measured by a particle size analyzer of about 0.2 μm to about 3 μm, for example, about 0.3 μm to about 2 μm, and a BET specific surface area of about 1 m ² / g to about ^{10 m} 2 / g, it may be, for example, about ^{1 m} 2 / g to about ^7m 2 / g, may be pure greater than about 99%. Within the above range, the thermoplastic resin composition is excellent in antibacterial properties, weather resistance and the like.

  In a specific example, the zinc oxide has an intensity ratio (B / A) of a peak A in a 370 nm to 390 nm region and a peak B in a 450 nm to 600 nm region when photoluminescence (Photo Luminescence) is measured, from about 0 to about 1, For example, it may be about 0.01 to about 0.09, or about 0.1 to about 1. Within the above range, the thermoplastic resin composition is excellent in antibacterial properties, low odor properties, weather resistance, and the like.

  In a specific example, at the time of X-ray diffraction (XRD) analysis, the zinc oxide has a peak position (peak position) 2θ value in the range of 35 ° to 37 ° and a measured FWHM value (diffraction value). The value of the crystallite size calculated by applying to the Scherrer's equation (Equation 1 below) based on the Full width at Half Maximum of the peak is about 1,000Å to about 2,000Å, For example, it may be about 1,200 ° to about 1,800 °. Within the above range, the thermoplastic resin composition is excellent in initial hue, weather resistance, antibacterial properties and the like.

  In the above formula 1, K is a shape factor, λ is an X-ray wavelength, β is a FWHM value (degree), and θ is a peak position value (peak position degree). ).

  In a specific example, the zinc oxide is formed by dissolving zinc in a metal form, heating to about 850 ° C. to about 1,000 ° C., for example, about 900 ° C. to about 950 ° C., vaporizing, and then injecting oxygen gas. To about 20 ° C. to about 30 ° C., and, if necessary, performing a heat treatment at about 700 ° C. to about 800 ° C. for about 30 minutes to about 150 minutes while injecting nitrogen / hydrogen gas into the reactor. It can be manufactured by cooling to room temperature (20 ° C. to 30 ° C.).

  In a specific example, the zinc oxide is used in an amount of about 0.01 to about 2 parts by weight, for example, about 0.02 to about 0.5 parts by weight, based on about 100 parts by weight of the thermoplastic resin. May comprise from about 0.03 parts to about 0.2 parts by weight. If the zinc oxide is used in less than about 0.01 part by weight, the antibacterial properties of the thermoplastic resin composition may be reduced. ) May be reduced.

  The thermoplastic resin composition according to one embodiment of the present invention may further include an additive contained in a general thermoplastic resin composition. Examples of the additives include a flame retardant, a filler, an antioxidant, an anti-dripping agent, a lubricant, a release agent, a nucleating agent, an antistatic agent, a stabilizer, a pigment, a dye, a mixture thereof, and the like. Not limited to When the above additive is used, its content is about 0.001 part by weight to about 40 parts by weight, for example, about 0.1 part by weight to about 10 parts by weight, based on about 100 parts by weight of the thermoplastic resin. obtain.

  The thermoplastic resin composition according to one embodiment of the present invention is prepared by mixing the above-mentioned components and melting at about 200 ° C. to about 280 ° C., for example, about 220 ° C. to about 250 ° C. using a conventional twin-screw extruder. It can be in extruded pellet form.

  In a specific example, the thermoplastic resin composition is inoculated with Staphylococcus aureus and Escherichia coli into a test piece having a size of 5 cm × 5 cm based on the JIS Z 2801 antibacterial evaluation method, and is inoculated at a temperature of 35 ° C. and an RH of 90%. After culturing for a period of time, the measured antimicrobial activity value may be about 2 to about 7 and about 2 to about 6.5, respectively.

In a specific example, the thermoplastic resin composition has a surface resistance value measured based on ASTM D257 of about 1 × 10 ⁶ Ω · cm to about 1 × 10 ¹⁰ Ω · cm, for example, about 1 × 10 ⁸ Ω · cm. cm to about 1 × 10 ¹⁰ Ω · cm.

  In a specific example, the thermoplastic resin composition has a notch Izod impact strength of a 1/4 ″ thick test piece measured based on ASTM D256 of about 15 kgf · cm / cm to about 25 kgf · cm / cm, for example, about 18 kgf. Cm / cm to about 23 kgfcm / cm.

  The molded article according to the present invention is formed from the above-mentioned thermoplastic resin composition. The thermoplastic resin composition can be manufactured in the form of pellets, and the manufactured pellets are manufactured into various molded products (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. can do. Such molding methods are well known to those of ordinary skill in the art to which this invention belongs. The above molded products are excellent in antibacterial properties, antistatic properties, impact resistance, transparency, fluidity (molding processability), balance of these physical properties, etc., so that there are many physical contact materials for medical supplies, electric / electronic Useful for interior / exterior materials of products.

  Hereinafter, the present invention will be described more specifically with reference to Examples. However, such Examples are for the purpose of explanation only, and should not be construed as limiting the present invention.

Examples The specifications of each component used in Examples and Comparative Examples are as follows.

(A) Thermoplastic resin (A1) Rubber-modified aromatic vinyl-based graft copolymer 55% by weight of styrene and acrylonitrile (weight ratio: 75/25) are grafted on 45% by weight of butadiene rubber having a Z-average of 310 nm. Co-polymerized g-ABS was used.

(A2) Aromatic vinyl copolymer resin (A2-1) A SAN resin (weight average molecular weight: 130,000 g / mol) obtained by polymerizing 71% by weight of styrene and 29% by weight of acrylonitrile was used.

  (A2-2) A methyl methacrylate-styrene-acrylonitrile copolymer (MSAN, weight average molecular weight: 90,000 g / mol) obtained by polymerizing 74% by weight of methyl methacrylate, 22% by weight of styrene, and 4% by weight of acrylonitrile was used. .

(B) Antistatic agent (B1) An antistatic agent containing a polyetheresteramide block copolymer (manufacturer: Sanyo, product name: PELECTRON AS) was used.

  (B2) Ultramide 8270HS from BASF was used.

(C) Zinc oxide Average particle diameter 1.2 μm, BET surface area 5.5 m ² / g, purity 99.9%, peak A in the 370 nm to 390 nm region and peak A in the 450 nm to 600 nm region when measuring photoluminescence (Photo Luminescence). Zinc oxide having an intensity ratio (B / A) to peak B of 0.28 and a crystallite size of 1,750 ° was used.

  (D) Titanium oxide (manufacturer: Kemira Specialty Corp, product name: WH-01) was used.

Measurement Methods of Physical Properties (1) Average particle size (unit: μm): The average particle size was measured using a particle size analyzer (a device of Beckman Coulter, Laser Diffraction Particle Size Analyzer LS I3 320).

(2) BET surface area (unit: m ² / g): The BET surface area was measured by a nitrogen gas adsorption method using a BET analyzer (Surface Area and Porosity Analyzer ASAP 2020 manufactured by Micromeritics).

  (3) Purity (unit:%): Purity was measured using TGA thermal analysis at the temperature of 800 ° C. and remaining weight.

  (4) PL intensity ratio (B / A): According to a photoluminescence (Photo Luminescence) measurement method, a spectrum obtained by injecting a 325 nm wavelength He-Cd laser (KIMMON, 30 mW) at room temperature into a test piece and emitting light at a CCD. Detection was performed using a detector. At this time, the temperature of the CCD detector was kept at -70 ° C. The intensity ratio (B / A) between the peak A in the 370 nm to 390 nm region and the peak B in the 450 nm to 600 nm region was measured. Here, the injection test piece was subjected to PL analysis by irradiating a laser to the test piece without performing a separate treatment, and the zinc oxide powder was put into a 6 mm diameter pelletizer, pressed and flattened. After preparing the piece, it was measured.

  (5) Crystallite size (unit: Å): peak position using high resolution X-ray diffraction analyzer (High Resolution X-Ray Diffractometer, manufacturer: X'pert, apparatus name: PRO-MRD) (Peak position) 2θ value is in the range of 35 ° to 37 °, and is applied to Scherrer's equation (Formula 1 below) based on the measured FWHM value (Full width at Half Maximum of the diffraction peak (peak)). Calculated. Here, both the powder form and the injection test piece can be measured. For more accurate analysis, in the case of the injection test piece, the polymer resin is removed by heat treatment at 600 ° C. in an air state for 2 hours. After that, XRD analysis was performed.

  In Equation 1, K is a shape factor, λ is an X-ray wavelength, β is a FWHM value (degree), and θ is a value of a peak position (peak position degree). ).

Examples 1 to 5 and Comparative Examples 1 to 6
Each of the above components was added at the contents shown in Tables 1 and 2 below, and extruded at 230 ° C. to produce pellets. Extrusion was carried out using a twin screw extruder having an L / D of 36 and a diameter of 45 mm. ) To produce a test piece. The physical properties of the manufactured test pieces were evaluated by the following methods, and the results are shown in Tables 1 and 2 below.

Measurement Methods of Physical Properties (1) Antibacterial activity value: Staphylococcus aureus and Escherichia coli were inoculated on a test piece having a size of 5 cm × 5 cm based on JIS Z 2801 antibacterial evaluation method, and were incubated at 35 ° C. and RH 90% for 24 hours. After culturing, measurements were taken.

  (2) Surface resistance value (unit: Ω · cm): Measured with a surface resistance measuring device (manufacturer: Mitsubishi Chemical, device name: Hiresta-UP (MCP-HT450)) based on ASTM D257.

  (3) Notch Izod impact strength (unit: kgf · cm / cm): Notch Izod impact strength was measured on a １ ／ ″ test piece based on ASTM D256.

  (4) Transparency (haze) (unit:%): Based on ASTM D1003, the transparency (haze) of a 2.5 mm-thick test piece was measured using a Haze meter NDH 2000 apparatus manufactured by Nippon Denshoku Co., Ltd. .

  From the above results, it was found that the thermoplastic resin composition of the present invention was excellent in antibacterial properties, antistatic properties, impact resistance, and the like.

  On the other hand, in the case of Comparative Example 1 in which a small amount of an antistatic agent was used, it was found that the antistatic property was reduced, the measured resistance value exceeded the measuring range, and the antibacterial property (Staphylococcus) was greatly reduced. In the case of Comparative Example 2 in which an excessive amount of the agent was used, it was found that the impact resistance was reduced. In the case of Comparative Example 3 in which a small amount of zinc oxide was used, it was found that the antibacterial property was greatly reduced, and In the case of Comparative Example 4 in which the amount was used, it was confirmed that the transparency was almost opaque. In addition, in the case of Comparative Example 5 in which the antistatic agent (B2) was applied, it was found that the antistatic properties, antibacterial properties, etc. were reduced, and in the case of Comparative Example 6, in which titanium oxide was applied as the antibacterial agent, the antibacterial properties were reduced. Was found to have greatly decreased.

  Simple variations or modifications of the present invention can be readily implemented by those having ordinary skill in the art, and both such modifications and changes can be considered to be included in the scope of the present invention.

Claims (11)

About 100 parts by weight of a thermoplastic resin containing a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin;
About 10 parts to about 30 parts by weight of an antistatic agent; and about 0.01 parts to about 2 parts by weight of zinc oxide;
A thermoplastic resin composition, wherein the antistatic agent contains at least one of a polyetheresteramide block copolymer, a polyalkylene glycol, and a polyamide.   The rubber-modified vinyl-based graft copolymer is characterized in that a monomer mixture containing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer is graft-polymerized to a rubbery polymer. 2. The thermoplastic resin composition according to 1.   The aromatic vinyl copolymer resin is a polymer of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer. The thermoplastic resin composition according to the above.   The rubber-modified vinyl-based graft copolymer is included in about 20% by weight to about 50% by weight of the thermoplastic resin of 100% by weight, and the aromatic vinyl-based copolymer resin is contained in the thermoplastic resin by 100% by weight. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises from about 50% to about 80% by weight of the composition. The zinc oxide has an average particle size is about 0.2μm~ about 3 [mu] m, a thermoplastic resin according to claim 1, wherein the BET specific surface area of about ^{1 m} 2 / g to about ^{10 m} 2 / g Composition.   The zinc oxide has an intensity ratio (B / A) of a peak A in a range of 370 nm to 390 nm and a peak B in a range of 450 nm to 600 nm of about 0 to about 1 upon measurement of photoluminescence (Photo Luminescence). The thermoplastic resin composition according to claim 1, wherein When the zinc oxide is analyzed by X-ray diffraction (XRD), a peak position 2θ value is in a range of 35 ° to 37 °, and a crystallite size according to the following equation 1 is obtained. The thermoplastic resin composition according to claim 1, wherein the value of the thermoplastic resin composition is from about 1,000 ° to about 2,000 °:

In Equation 1, K is a shape factor, λ is an X-ray wavelength, β is a FWHM value (degree) of an X-ray diffraction peak, and θ is It is a value of a peak position (peak position degree).   The thermoplastic resin composition was measured by inoculating Staphylococcus aureus and Escherichia coli into a test piece having a size of 5 cm × 5 cm according to JIS Z 2801 antibacterial evaluation method, and culturing at 35 ° C. and RH 90% for 24 hours, followed by measurement. The thermoplastic resin composition of claim 1, wherein the antimicrobial activity values are about 2 to about 7 and about 2 to about 6.5, respectively. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a surface resistance value of about 1 × 10 ⁶ Ω · cm to about 1 × 10 ¹⁰ Ω · cm measured according to ASTM D257. Thermoplastic resin composition.   The thermoplastic resin composition is characterized in that a notch Izod impact strength of a 1/4 "thick test piece measured according to ASTM D256 is about 15 kgf · cm / cm to about 25 kgf · cm / cm, The thermoplastic resin composition according to claim 1.   A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 10.